JPH039948A - Polyester composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] <Industrial Application Field> The present invention relates to a polyester composition that has good heat resistance, excellent retention stability during molding, high cycle performance, and good dry heat deterioration resistance. It is.

<Conventional technology> Polycyclohexane dimethylene terephthalate (hereinafter referred to as P
In addition to its excellent mechanical properties and chemical resistance, CT (abbreviated as CT) has a higher heat distortion temperature than conventional polyesters such as polybutylene terephthalate and polyethylene terephthalate. It is expected to be used for applications such as electric/electronic equipment parts, automobile parts, and mechanical parts. However, P.C.
Since the degree of polymerization of T tends to decrease during molding, the mechanical properties also deteriorate due to short stays in molding, and it also has problems such as poor hydrolysis resistance and dry heat deterioration resistance. However, it was difficult to put it into practical use as a molding material.

To solve these problems, it is conceivable to apply the method applied to polyethylene terephthalate, which is a similar terephthalic acid polyester, as is. Typical examples of such methods include a method of adding diglycidyl ethers such as bisphenol A epoxy resin (Japanese Unexamined Patent Publication No. 134789/1989) and a method of adding diglycidyl esters such as diglycidyl terephthalate ( (Japanese Patent Application Laid-Open No. 55-82148)
Examples include.

<Problems to be Solved by the Invention> However, although these methods may prevent the apparent viscosity reduction of PCT, the mechanical properties still deteriorate, and the dry heat deterioration resistance also deteriorates significantly. However, an effective method to truly prevent the decrease in the degree of polymerization during PCT retention, to exhibit its original high mechanical properties, and to improve dry heat deterioration resistance has yet to be found. There wasn't.

As a result of intensive study by the present inventors to solve the above problems,
P with a cyclohexane ring of a specific cis/trans ratio
We have discovered that by incorporating a specific amount of a specific glycidyl ester ether into CT, the above problems can not only be solved, but also the crystallization rate can be improved and a polyester composition with excellent high cycle properties can be obtained. , arrived at the present invention.

<Means for Solving the Problems> That is, the present invention provides 0.005 to 1 part of an epoxy compound represented by the following general formula (1) to 100 parts by weight of polycyclohexane dimethylene terephthalate polyester.
0 parts by weight, the cis/trans ratio (molar ratio), which is the ratio of the cis structure to the trans structure of the cyclohexane ring in the polycyclohexane dimethylene terephthalate polyester, is from 60/40 to
The object of the present invention is to provide a polyester composition characterized in that the polyester composition is in the range of 10/90.

\. / (However, in the formula, R represents a hydrocarbon group having 6 to 30 carbon atoms, n
represents O or an integer from 1 to 20. ) The method for producing polycyclohexane dimethylene terephthalate polyester in the present invention is not particularly limited, but for example, in the presence or absence of a catalyst such as an organic titanium compound, terephthalic acid or a lower alkyl ester thereof and cis/ A method of polycondensing 1,4-cyclohexane dimetatool with a trans ratio of 50,150 to 10/90 (molar ratio) is exemplified. As the polymerization conditions, for example, the conditions described in US Pat. No. 2,901,466 can be applied.

The acid component or diol component of polycyclohexane dimethylene terephthalate polyester is 20 mol% or less,
Preferably in a range of 10 mol% or less, isophthalic acid, orthophthalic acid, 2.6-naphthalenedicarboxylic acid, 2.
7-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, methyl terephthalic acid, 4,4°-biphenyl dicarboxylic acid, 2,2-biphenyl dicarboxylic acid, 1
．． Other dicarboxylic acids such as 2-bis(4-carboxyphenoxy)-ethane, succinic acid, adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, octadecanedicarboxylic acid, dimer acid and 1,4-cyclohexanedicarboxylic acid acid or ethylene glycol,
Propylene glycol, 1,5-pentanediol, 1
．． 6-hexanediol, 1.8-octanediol,
1,10-decanediol, 1,3-cyclohexane dimetatool, 1,2-cyclohexane dimetatool and 2,2-bis(2-hydroxyethoxyphenyl)
Substitutions with other diols such as propane can also be used.

The cyclohexane ring, which is a part of the 1,4-cyclohexanedimethanol residue of the polycyclohexane dimethylene terephthalate polyester used in the present invention, has a cis/trans ratio (molar ratio), which is the ratio of cis structure to trans structure, of 60. It is preferably in the range of /40 to 10/90, more preferably in the range of 50,150 to 15/85, particularly preferably in the range of 40/60 to 25/75. Sis/
If the trans ratio is 60/40 or more, the melting point of the polyester will be low, making it difficult to apply it to applications that require heat resistance.On the other hand, if the trans ratio is less than 10/90, the melting point of the polyester will be too high. The difference between the decomposition temperature and the molding temperature becomes small, and even with the technique of the present invention, it becomes difficult to improve the retention stability during molding.

The polycyclohexane dimethylene terephthalate polyester used in the present invention preferably has an intrinsic viscosity of 0.4 to 2.0 cull/f, more preferably 0 when a 0.5% 0-chlorophenol solution is measured at 25°C. ．．
5-1. OdJ/g is desirable. The intrinsic viscosity here is expressed by the following formula (I).

,l! nt t.

Intrinsic viscosity = . ...(II> (In the formula, C is the concentration expressed in grams of polycyclohexane dimethylene terephthalate polyester per 100 ml of solution, to is the solvent flow time, and t is the solution flow time.) Polycyclohexane di If the intrinsic viscosity of the methylene terephthalate polyester is less than 0.4 dN/g, the mechanical properties will be poor, while if it exceeds 2.0 dN/g, the moldability will tend to be poor, both of which are not preferred.

Further, the terminal carboxyl group weight of the polycyclohexane dimethylene terephthalate polyester is preferably 30 equivalents/10', -polymer or less after addition of the epoxy compound, but in order to satisfy this condition, it is necessary to It is desirable that the value is 100 equivalents/106 g of polymer or less.

The amount of terminal carboxyl groups of the polycyclohexane dimethylene terephthalate polyester is, for example, Anal,
It can be measured using the method of H, A, and Poh described in Chem., 2nd Edition, 1614-1616 (1954).

Next, the epoxy compound used in the present invention has the general formula (
I>. R is a hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. Specific examples of R are 1, 4
-Phenylene, 1,3-phenylene, 1,2-phenylene, 2-methyl-1,4-phenylene, 4,4-biphenylene, 3.3゛-biphenylene, 2.2゛-biphenylene, 3,4゛- Biphenylene, 1,4-naphthylene,
1.5-naphthylene, 2.6-naphthylene, 2.7-naphthylene, 1.4-cyclohexylene, 1.3-cyclohexylene, 1.2-cyclohexylene, 4,4-bicyclohexylene, 2.6 Preferred examples include decahydronaphthylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, pentadecamethylene, heptadecamethylene, octadecamethylene and 2゜6-dimethylhebutamethylene. Particularly preferred are 1,4-phenylene, 1,3-phenylene and 2,6-naphthylene.

(I> The value of the degree of polymerization n of the compound of formula is 0 or an integer of 1 to 20, preferably 0 or an integer of 1 to 10, and may be a mixture of compounds having various degrees of polymerization.

Particularly preferred is an average degree of polymerization in the range of 0 to 2, and a ratio of weight average degree of polymerization (Pw) to number average degree of polymerization (Pn), Pw/Pn, in the range of 1.0 to 3.0. It is something.

(I> The method for producing the epoxy compound represented by the formula is not particularly limited, but for example, hydroxycarboxylic acid and shrimp halohydrin are mixed in the presence of a catalyst such as a quaternary ammonium salt, a tertiary amine, or a tertiary phosphine, 40℃~1
Examples include a method of producing by reacting at 50'C to perform halohydrin ester etherification, and then adding an alkali metal hydroxide to dehydrohalogenate. A product having a high degree of polymerization can be obtained by further reacting a hydroxycarboxylic acid in the presence of a catalyst at an appropriate ratio.

In the present invention, the amount of the epoxy compound represented by formula (I) added is 0.005 to 10 parts by weight per 100 parts by weight of polycyclohexane dimethyl I/nterephthalate polyester.
Parts by weight are preferred, preferably 0.05 to 5 parts by weight, more preferably 0.1 to 3 parts by weight. When the amount added is 0.005 parts by weight with no grooves, the improvement effect on molding retention stability, dry heat deterioration resistance, etc. is small, while when it exceeds 10 parts by weight, the mechanical properties of the polycyclohexane dimethylene terephthalate polyester are Both are undesirable because they impair the properties.

Further, the amount of the epoxy compound of formula (I) to be added is such that after addition to polycyclohexane dimethylene terephthalate, the amount of terminal carboxyl groups of polycyclohexane dimethylene terephthalate is 30 equivalents/106 g-polycyclohexane dimethylene terephthalate polymer or less. It is preferable to add it in a proportion as high as possible from the viewpoint of improving molding fluidity, retention stability, dry heat deterioration resistance, etc.

It is a preferred method to include reinforcing fillers in the compositions of the present invention. Even when a reinforcing filler is added, the epoxy compound of the present invention exhibits the same effects as when no reinforcing filler is added. Such reinforcing fillers mean fibrous and granular fillers, such as glass fibers, glass peas, glass flakes, carbon fibers, ceramic fibers, asbestos, wollastenite, talc, clay, mica, sericite, zeolites. , bentonite, dolomite, kaolin, finely divided silicic acid, feldspar powder, potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, aluminum silicate, silicon oxide, gypsum, tubaculite, Examples include dawsonite and white clay, and two or more types of these can also be used in combination. Among these reinforcing fillers, glass fiber, glass beads, wollastenite, mica, clay, and talc are particularly suitable for use.

The amount of these reinforcing fillers added is 1 to 150 parts by weight based on 100 parts by weight of polycyclohexane dimethylene terephthalate.

In addition to the epoxy compound of the present invention, the composition of the present invention may contain other epoxy compounds, oxazoline compounds, carbodiimide compounds, aziridine compounds, and other compounds that further improve the hydrolysis resistance of polyester.

The composition of the present invention includes, to the extent that the object of the present invention is not impaired,
It may further contain at least one of the usual additives such as antioxidants, UV absorbers, heat stabilizers, lubricants, mold release agents, colorants including dyes and pigments, nucleating agents and flame retardants. .

Additionally, small amounts of other thermoplastic resins (e.g. polyethylene, acrylic resins, fluororesins, polyamides, polyethylene terephthalate resins, polybutylene terephthalate resins,
Polyphenylene sulfide resin, polyether ether ketone resin, liquid crystal polyester resin, polyacetal, polycarbonate, polysulfone, polyphenylene oxide, etc.), thermosetting resin (e.g. phenol resin, melamine resin, polyester resin, silicone resin,
epoxy resins, etc.) and soft thermoplastic resins (e.g., ethylene/vinyl acetate copolymers, polyester elastomers, ethylene/propylene terpolymers, etc.).

Although the method for producing the composition of the present invention is not particularly limited, it is preferable to add the polycyclohexane dimethylene terephthalate polyester, the epoxy compound, and other additives as necessary at a temperature equal to or higher than the melting point of the polycyclohexane dimethylene terephthalate polyester. Examples include a method of melt-kneading a homogeneous mixture using an extruder.

The obtained composition can be molded by any commonly known method such as injection molding or extrusion molding.

Molded articles obtained from the composition of the present invention have excellent mechanical properties and chemical resistance, and can be used for various purposes such as electrical/electronic parts, automobile parts, precision equipment parts such as mechanical parts, etc. I can do it.

<Example> The present invention will be explained in further detail with reference to Examples below.

Note that all parts in the examples are based on weight.

Examples 1-5. Comparative Examples 1 to 6 Poly-1,4-cyclohexane dimethylene terephthalate polyesters (PC
For 100 parts of one type of T), the following epoxy compound (B
After tri-blending the amounts listed in Table 1 of -1) to (B-7>), melt mixing and pelletization were performed using a screw extruder set at the temperature shown in Table 1. The melt flow rate (MFR>) was measured using an indexer at the melt processing temperatures listed in Table 1.The pellets were also subjected to an injection molding machine with an injection capacity of 5 ounces, and the melt processing temperatures and mold temperatures listed in Table 1 were
0℃, molding cycle (injection time/cooling time/intermediate time)
Molding was performed at 10 seconds/15 seconds/10 seconds (molding cycle (a)) to obtain a 1/8" test piece for tensile impact test and a test piece for measuring heat distortion temperature.

In addition, to investigate the influence of molding residence time, we also conducted a molding cycle (
Injection time/cooling time/intermediate time) 10 seconds/15 seconds/2
A test piece was obtained by molding in the same manner as above, except that the molding cycle was changed to 00 seconds (molding cycle (b)), and the other conditions were the same.

ASTM D6 for test pieces of molding cycle (a)
48, and measure the heat distortion temperature at 180℃ x 20
A tensile impact test was performed according to ASTM D1822 before and after the 1-day dry heat test to determine the tensile impact strength.

Moreover, the tensile impact strength was similarly determined for the test piece of the molding cycle (b).

[PCT] Cis/trans ratio of A-1 dichlorohexanedimetatool residue = 35/65, intrinsic viscosity 0.81. Terminal carboxyl group weight 3 7 equivalents 7106 g - Polymer A-2: cis/trans ratio = 49151, intrinsic viscosity 0
．． 78 A-3: cis/trans ratio = 20/80, intrinsic viscosity 0.
84, 5 mol% isophthalic acid copolymer A-4 as acid component: cis/trans ratio = 70/30, intrinsic viscosity 0.
78゜A-5: cis/trans ratio = 6/94, intrinsic viscosity 0.8
0 [Epoxy compound] ＼. / \. / \. / \. / B-7: Diglycidyl terephthalate As is clear from the results in Table 1, PCT containing a specific epoxy compound as a repeating unit of a cyclohexane dimetatool residue having a specific cis/trans ratio The composition of the present invention has a high heat distortion temperature and exhibits little decrease in viscosity and physical properties during residence, and also exhibits little decrease in physical properties during heat treatment.

Examples 6-10. Comparative Examples 7 to 12 100 parts of PCT shown in Table 2 was triblended with 50 parts by weight of an epoxy compound of the type and amount shown in Table 2 and glass fiber (3 parts m length, 11 μm diameter, chopped strand type). After that, melt extrusion and molding evaluation were performed in the same manner as in Example 1 except that the melt processing temperatures listed in Table 2 were applied.

In order to further evaluate the formability, the length is 10011! I11, width 5011IIm, depth 30m-1 wall thickness 2! A small box of 11 m was molded, and the minimum molding cycle time that could be molded without deformation was determined and used as a measure of moldability. However, the cylinder temperature was set to the melt processing temperature listed in Table 2, and the mold temperature was 120°C.

These results are shown in Table 2.

As is clear from the results in Table 2, even when glass fiber is blended, a specific epoxy compound is contained in PCT having a cyclohexane dimetatool residue with a specific cis/trans ratio as a repeating unit. It can be seen that the composition of the present invention, which has a high heat distortion temperature, shows less decrease in viscosity and physical properties during residence, less decrease in physical properties during heat treatment, and also has a shorter molding cycle. On the other hand, such effects cannot be obtained when using other epoxy compounds other than the present invention, such as diglycidyl ether type or diglycidyl ester type.

<Effects of the Invention> The molded product obtained from the polyester composition of the present invention has high heat resistance, excellent retention stability during molding and high cycle performance, and good dry heat deterioration resistance, and is suitable for electrical and electronic equipment parts. It is useful as automobile parts, machine/mechanical parts, etc.

Patent application Daitoshi Co., Ltd.

Claims (1)

[Scope of Claims] A composition comprising 0.005 to 10 parts by weight of an epoxy compound represented by the following general formula (I) based on 100 parts by weight of polycyclohexane dimethylene terephthalate polyester, comprising: A polyester composition characterized in that the cis/trans ratio (molar ratio), which is the ratio of the cis structure to the trans structure of the cyclohexane ring in the polycyclohexane dimethylene terephthalate-based polyester, is in the range of 60/40 to 10/90. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ …(I) (However, in the formula, R is a hydrocarbon group with 6 to 30 carbon atoms , n
represents 0 or an integer from 1 to 20. )